CN109192522B - Fe2O3Nano carbon tube composite material, preparation method thereof and super capacitor - Google Patents

Fe2O3Nano carbon tube composite material, preparation method thereof and super capacitor Download PDF

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CN109192522B
CN109192522B CN201810887727.4A CN201810887727A CN109192522B CN 109192522 B CN109192522 B CN 109192522B CN 201810887727 A CN201810887727 A CN 201810887727A CN 109192522 B CN109192522 B CN 109192522B
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composite material
carbon nanotube
carbon
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carbon nanotubes
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CN109192522A (en
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徐军明
杨成明
李苗
姚亚
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Jiashan National Innovation Energy Research Institute
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Hangzhou Dianzi University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses Fe2O3Nano-carbon tube composite material, preparation method thereof and super capacitor, wherein nano Fe2O3The weight ratio of the Fe-Fe alloy in the composite material is 50-60 percent2O3The diameter of the nano particles is less than 10nm, and the nano particles are uniformly loaded on the surface of the carbon nano tube. By adopting the technical scheme of the invention, the performance of the material on the super capacitor is as follows: the total weight of the composite material is taken as the weight of the active substance, the highest specific capacity can reach 940F/g under the voltage window of-1.2V to-0.4V and the constant current charging and discharging of 2A/g, the composite material has good rate capability, and the specific capacity can reach under the current of 4, 6, 8, 10, 12 and 15A/g: 873, 834, 796, 754, 711 and 645 mAh/g. The capacity characteristic and rate capability of the composite material reach the best ferric oxide composite material at present.

Description

Fe2O3Nano carbon tube composite material, preparation method thereof and super capacitor
Technical Field
The invention relates to the technical field of nano composite materials, in particular to Fe2O3A nano carbon tube composite material, a preparation method thereof and a super capacitor.
Background
The super capacitor is also called electrochemical capacitor, and is a novel energy storage device between the traditional capacitor and a rechargeable battery. It has the features of fast charge and discharge and has the energy storing mechanism of electrochemical cell. Compared with the traditional capacitor, the super capacitor has the characteristics of high power density, long cycle life, no pollution, wider working temperature range and the like. The carbon material with high specific surface area is mainly adopted in the currently marketed super capacitor, and the carbon material mainly depends on the electric double layer capacitance for energy storage, and the specific capacitance needs to be further improved. The hot spot of research is to use metal oxide as super capacitor material, which can generate larger pseudocapacitance and thus has higher specific capacitance than carbon material.
The pseudocapacitance mainly relied on by the metal oxide as the super capacitor material is the oxidation-reduction reaction of metal ions. This reaction occurs mainly at the interface with the electrolyte. Therefore, in order to obtain a high specific capacitance, it is necessary to prepare a metal oxide having a nano-scale to increase a specific surface area. At the same time, reducing the size of the metal oxide also facilitates rapid charge transfer from the metal oxide to the electrode. Therefore, how to prepare metal oxide nanoparticles with small particle size and without agglomeration becomes the focus of research.
Fe2O3Has the advantages of wide material, low price, environmental protection and the like, and is a promising super capacitor electrode material. At the same time, Fe2O3The oxidation-reduction potential of the composite material is lower, the composite material is the most main negative electrode material for preparing the asymmetric super capacitor, and the performance of the composite material is improved, so that the preparation of the asymmetric super capacitor is facilitated. But causes volume expansion due to the occurrence of redox reaction, thereby causing poor cycle performance and stability. The main study is currently through Fe2O3The subject group also discloses a preparation method for preparing iron oxide nanoparticles on multilayer graphene by adopting a hydrothermal method in a patent Z L201510733408.
Therefore, it is necessary to provide a technical solution to solve the technical problems of the prior art.
Disclosure of Invention
In view of the above, it is necessary to provide Fe with good electrochemical performance and easy industrialization2O3A nano carbon tube composite material, a preparation method thereof and a super capacitor.
In order to solve the technical problems in the prior art, the technical scheme of the invention is as follows:
fe2O3Nano carbon tube composite material, nano Fe2O3The weight ratio of the Fe-Fe alloy in the composite material is 50-60 percent2O3The diameter of the nano particles is less than 10nm, and the nano particles are uniformly loaded on the surface of the carbon nano tube.
As a preferred technical solution, the carbon nanotubes are multi-walled carbon nanotubes.
The invention also discloses Fe2O3The preparation method of the/carbon nanotube composite material comprises the following steps:
step S1: measuring DMF and distilled water, and uniformly mixing to obtain a mixed solvent;
s2, weighing a certain amount of carbon nanotubes, adding the carbon nanotubes into the mixed solvent prepared in the S1, and uniformly dispersing the carbon nanotubes in the solvent by ultrasonic waves to obtain carbon nanotube dispersion liquid, wherein the concentration of the carbon nanotubes in the mixed liquid is 0.5-2 mg/m L;
step S3, weighing ferrous chloride tetrahydrate and anhydrous sodium acetate, adding the ferrous chloride tetrahydrate and the anhydrous sodium acetate into the carbon nanotube dispersion liquid prepared in the step S2, uniformly stirring and mixing the mixture by magnetic force, adjusting the pH value of the mixed liquid to 6 by HCl with the concentration of 5%, then putting the mixed liquid into a 60-90-degree water bath kettle, and continuing stirring in a water bath manner, wherein the concentration of the ferrous chloride tetrahydrate relative to the concentration of the mixed liquid is 8-12 mg/m L, and the molar concentration ratio of the anhydrous sodium acetate relative to the ferrous chloride tetrahydrate is 2: 1-5: 1;
step S4: cooling, centrifugally cleaning to collect black product, and drying to obtain Fe2O3A carbon nanotube composite material.
As a preferable technical scheme, the volume ratio of DMF to distilled water in the mixed solvent prepared in the step S1 is 8: 2.
As a preferable embodiment, in step S2, a multi-walled carbon nanotube is used as the carbon nanotube.
Preferably, in step S2, the ultrasonication time is 3 hours.
As a preferable technical solution, the step S4 further includes a step of centrifugal washing, wherein,
the centrifugal cleaning adopts 3 times of deionized water and 3 times of alcohol centrifugal cleaning, and the speed of a centrifugal machine is 6000 r/min;
after centrifugal cleaning, drying for 12 hours by using a 60-degree oven.
Preferably, in step S3, the stirring speed of the water bath is 300 rpm, the temperature of the water bath is 60-90 ℃, and the stirring time is 2-5 hours.
The invention also discloses a super capacitor, adopting Fe in claims 1-82O3The/nanometer carbon tube composite material is used as the cathode material of the super capacitor.
Compared with the prior art, the invention has the following technical effects:
(1) in the composite structure, the diameter of the nano iron oxide particles is small, so that the contact area of the iron oxide and the electrolyte is increased, the activity of the nano iron oxide is improved, the redox current of the iron oxide is improved, and the specific capacitance of the composite material is improved.
(2) The carbon nano-tubes play a role of a conductive network, the nano-iron oxide is in contact with the carbon nano-tubes, the particle size of the nano-iron oxide is small, and the charge transfer speed can be improved, so that the performance of the composite material under high rate is improved.
(3) The carbon nanotube has a large surface area and can well support the nano iron oxide.
(4) The diameter and the wall thickness of the carbon nano-tube are not required, and the composite material can be prepared. The carbon nanotubes need not be subjected to special treatment such as oxidation treatment or surface introduction of functional groups, and can be dispersed by ultrasonic dispersion.
(5) The preparation process is simple and the preparation cost is low. The preparation temperature can be as low as 60 ℃, and the optimal temperature is 70 ℃. The preparation time is short, and the product can be obtained within 2-5 hours. No post-treatment is required after preparation. Therefore, the composite material has high preparation efficiency and low preparation cost, and is suitable for large-scale production.
(6) The prepared composite material has good oxidation-reduction reaction characteristics and has an obvious charge-discharge platform in the constant-current charge-discharge process.
(7) The prepared composite material has the optimal specific capacity up to 930F/g and good rate capability. Can be achieved under the conditions of 2, 4, 6, 8 and 10A/g. The capacity characteristic and rate capability of the composite material exceed those of the currently best iron oxide composite material.
Drawings
FIG. 1 is Fe2O3XRD pattern of/carbon nanotube composite material.
FIG. 2 is Fe2O3SEM image of/carbon nanotube composite material.
FIG. 3 is Fe2O3TEM image of/carbon nanotube composite.
FIG. 4 is Fe2O3CV curve of/nano carbon tube composite material electrode.
FIG. 5 is Fe2O3The/nanometer carbon tube composite material electrode has constant current charge and discharge curve under different current density.
FIG. 6 is Fe2O3Multiplying power curve of the nano carbon tube composite material electrode.
FIG. 7 is Fe2O3EIS curve of/carbon nanotube composite material electrode.
FIG. 8 shows Fe2O3Flow diagram of the preparation method of the/carbon nanotube composite material.
The following specific embodiments will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The technical solution provided by the present invention will be further explained with reference to the accompanying drawings.
In order to improve the performance of the super capacitor, the invention compounds the ferric oxide on the surface of the carbon nano-tube, thereby further improving the performance of the composite material. The carbon nanotubes do not need to be activated, and the diameter and the number of layers of the carbon nanotubes are not required, so that the process is simplified. However, the applicant found in the research that the preparation method of the prior art can not be transplanted to the preparation of the composite material of the carbon nano-tube. The reason for this is mainly that carbon nanotubes have curved surfaces, and their van der waals force is smaller than that of multilayer graphene. The deposition speed of the ferric oxide in the prior art is too high, and the ferric oxide is difficult to deposit on the surface of the carbon nanotube. Therefore, the original method is not suitable for preparing the ferric oxide/nano carbon tube composite material.
For this purpose, the applicant modified the process, see fig. 8, for a Fe of the invention2O3The flow diagram of the preparation method of the carbon nanotube composite material comprises the following steps:
step S1: measuring DMF and distilled water, and uniformly mixing to obtain a mixed solvent;
s2, weighing a certain amount of carbon nanotubes, adding the carbon nanotubes into the mixed solvent prepared in the S1, and uniformly dispersing the carbon nanotubes in the solvent by ultrasonic waves to obtain carbon nanotube dispersion liquid, wherein the concentration of the carbon nanotubes in the mixed liquid is 0.5-2 mg/m L;
step S3, weighing ferrous chloride tetrahydrate and anhydrous sodium acetate, adding the ferrous chloride tetrahydrate and the anhydrous sodium acetate into the carbon nanotube dispersion liquid prepared in the step S2, uniformly stirring and mixing the mixture by magnetic force, adjusting the pH value of the mixed liquid to 6 by HCl with the concentration of 5%, then putting the mixed liquid into a 60-90-degree water bath kettle, and continuing stirring in a water bath manner, wherein the concentration of the ferrous chloride tetrahydrate relative to the concentration of the mixed liquid is 8-12 mg/m L, and the molar concentration ratio of the anhydrous sodium acetate relative to the ferrous chloride tetrahydrate is 2: 1-5: 1;
step S4: cooling, centrifugally cleaning to collect black product, and drying to obtain Fe2O3A carbon nanotube composite material.
The preparation principle of the invention is as follows: the iron ion forms complex in the solution, the complex of the iron ion is absorbed by the action of molecular force on the surface of the carbon nano-tube, and the complex is finally decomposed into ferric oxide. The invention has creative improvement in three aspects, 1, the low-temperature reaction is adopted, and the optimal composite material can be obtained at 70 ℃, which is the lowest preparation temperature of the iron oxide and carbon material composite material at present. Due to the low reaction temperature, the speed of the complex generated by the iron ions and DMF is limited, and the complex is decomposed slowly, so that the complex can be adsorbed on the surface of the carbon nano-tube. Therefore, the metal adsorbed on the surface of the carbon nano-tube is less in complexation, and the obtained iron oxide has small particles. 2. The water bath method is adopted, which is different from the hydrothermal method in the prior art, firstly, the water bath method can greatly reduce the requirements on equipment, thereby greatly saving the cost. Meanwhile, hydrothermal reaction generates pressure, thereby accelerating the reaction. And the water bath method can reduce the reaction acceleration problem caused by pressure. 3. With a stirring speed of 300 revolutions per minute, it was found experimentally that both too low a stirring speed and too high a stirring speed affected the preparation of the composite material. Too high a stirring speed makes the iron oxide nanoparticles easily fall off from the carbon nanotubes, while too low a stirring speed easily causes the iron oxide not to deposit on the carbon nanotubes, thereby causing the iron oxide to be separated out alone. 4. The pH of the solution was adjusted to 6 with HCl. The pH is adjusted to around this value, again to control the deposition and growth rate of the iron oxide. The above aspects play a common role in the invention, and the iron oxide nanoparticles and the carbon nanotubes are organically combined together, so that the composite material of the iron oxide nanoparticles and the carbon nanotubes with a good structure, which is obtained by the invention, is finally prepared. This organic combination is an inventive discovery of the present invention, making this method suitable for the uniform precipitation of iron oxide nanoparticles on the surface of carbon nanotubes.
Therefore, by adopting the technical scheme, a good iron oxide/carbon nanotube composite material can be prepared, a composite material with good structural characteristics is obtained, and the electrochemical performance is very excellent in application of a negative electrode material on a supercapacitor material.
The prepared iron oxide/carbon nanotube has the main structural characteristics that: the diameter of the nano ferric oxide particles is less than 10nm, and the nano ferric oxide particles are uniformly distributed on the surface of the carbon nano tube. The weight ratio of the nano ferric oxide in the composite material is 50-60%. The performance characteristics of the material on the super capacitor are as follows: the total weight of the composite material is taken as the weight of the active substance, the highest specific capacity can reach 940F/g under the voltage window of-1.2V to-0.4V and the constant current charging and discharging of 2A/g, the composite material has good rate capability, and the specific capacity can reach under the current of 4, 6, 8, 10, 12 and 15A/g: 873, 834, 796, 754, 711 and 645 mAh/g. The capacity characteristic and rate capability of the composite material reach the best ferric oxide composite material at present.
The technical scheme of the invention is detailed by the following embodiments.
Example 1:
(1) DMF 8m L and distilled water 2m L were weighed and mixed uniformly to obtain a mixed solvent.
(2) Weighing 20mg of carbon nanotubes, adding the carbon nanotubes into a mixed solution of DMF and distilled water, and performing ultrasonic treatment for 3 hours to uniformly disperse the carbon nanotubes in a solvent to obtain a carbon nanotube dispersion solution, wherein the concentration of the carbon nanotubes in the mixed solution is 2mg/m L.
(3) Weighing 100mg of ferrous oxide tetrahydrate and 200mg of anhydrous sodium acetate, magnetically stirring for 10 minutes, adjusting the pH value of the mixed solution to 6 by 5% of HCl, then putting the mixed solution into a 70-DEG water bath, and continuously magnetically stirring at a stirring speed of 300 revolutions per minute for 2 hours, wherein the concentration of the ferrous chloride tetrahydrate is 10mg/m L relative to that in the mixed solution, and the molar concentration ratio of the anhydrous sodium acetate to the ferrous chloride tetrahydrate is 4.878: 1.
(4) After cooling, the black product was collected by centrifugal washing with deionized water 3 times and alcohol 3 times. Drying to obtain Fe2O3A carbon nanotube supercapacitor material.
The sample obtained by the method is subjected to X-ray diffraction diffractometer (XRD) analysis, the obtained XRD spectrum is shown in figure 1, and the graphite peak and Fe of the carbon nanotube can be seen from the spectrum2O3The diffraction peak of (1). And Fe2O3The diffraction peak of (A) is wide, and Fe can be obtained from the Sheberry fraction2O3Has a small diameter. Fe can also be obtained from the Xiele formula2O3Is about 6nm in diameter.
The composite material was observed by Scanning Electron Microscope (SEM) to obtain an SEM image as shown in FIG. 2, from whichIt is seen that the surface of the carbon nanotube is uniformly covered with nano-Fe2O3Particles, carbon nanotubes due to the presence of nano-Fe2O3Are separated from each other and are uniformly distributed.
The composite material was observed by a Transmission Electron Microscope (TEM), and a TEM image is obtained as shown in fig. 3, from which it can be seen that nano iron oxide was attached to the surface of the carbon nanotube. The particle size of the nano ferric oxide is about 6 nm.
Mixing the obtained Fe2O3The/carbon nanotube composite material is used as an active material, the active material, acetylene black serving as a conductive agent and PVDF serving as a binder are placed into a crucible according to the mass ratio of 80:10:10, NMP serving as a dispersing agent is added, the mixture is mixed and stirred for 12 hours, and then the stirred slurry is uniformly coated on the treated foamed nickel, wherein the coating area is 1 × 1cm2And controlling the content of the active substance to be 5mg, and finally drying at 80 ℃ to evaporate the dispersant to obtain the required supercapacitor electrode.
The prepared electrode is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a mercury oxide electrode is used as a reference electrode to assemble a three-electrode system, a model CHI660e electrochemical workstation is adopted to test a cyclic voltammetry curve (CV curve) and alternating current impedance of the three-electrode system, and a blue super-capacitor tester is adopted to perform constant current charge and discharge tests. The tests were based on the total weight of the composite as the active weight.
Fig. 4 is a CV curve measured at different scan speeds, from which it can be seen that the composite material has a significant redox peak. The redox potential was-0.62 and-1.12V relative to the Ag/AgCl electrode at a scan rate of 5 mV/s. The redox potential is low, so that the material can be used as an anode material of an ultra-polar capacitor.
Fig. 5 is a constant current charge and discharge curve under different multiplying factors, and it can be seen that the charge and discharge platform is very obvious under low current density. At high current densities, a significant charge and discharge plateau was still seen. The composite material is proved to have excellent oxidation-reduction performance. Fig. 6 is the rate capability of the composite material, and it can be seen that the specific capacity can reach the following values at currents of 2, 4, 6, 8, 10, 12 and 15A/g: 940. 873, 834, 796. 754, 711 and 645 mAh/g. The composite material has good rate capability. The mass of the carbon nanotube before and after the growth of the iron oxide is weighed, and the weight of the iron oxide in the composite material is only 55 percent of the total weight. The multilayer graphite has low theoretical specific capacity, and the main specific capacity is Fe2O3A contribution. Therefore, the iron oxide in the composite material shows good redox characteristics.
Fig. 7 is an EIS curve of the composite material, from which it can be seen that the composite material has a very fast charge transfer rate and a low internal resistance.
Example 2:
(1) DMF 8m L and distilled water 2m L were weighed and mixed uniformly to obtain a mixed solvent.
(2) Weighing 10mg of carbon nanotubes, adding the carbon nanotubes into a mixed solution of DMF and distilled water, and performing ultrasonic treatment for 3 hours to uniformly disperse the carbon nanotubes in a solvent to obtain a carbon nanotube dispersion solution, wherein the concentration of the carbon nanotubes in the mixed solution is 1mg/m L.
(3) Weighing 120mg of ferrous oxide tetrahydrate and 247.5mg of anhydrous sodium acetate, namely the concentration of the ferrous chloride tetrahydrate is 12mg/m L relative to the concentration of the mixed solution, the molar concentration ratio of the anhydrous sodium acetate relative to the ferrous chloride tetrahydrate is 5:1, magnetically stirring for 10 minutes, adjusting the pH value of the mixed solution to 6 by 5% of HCl, then putting the mixed solution into a 60-DEG water bath, and continuing to magnetically stir at the stirring speed of 300 revolutions per minute for 3 hours.
(4) After cooling, the black product was collected by centrifugal washing with deionized water 3 times and alcohol 3 times. Drying to obtain Fe2O3A carbon nanotube supercapacitor material.
Example 3:
(1) DMF 8m L and distilled water 2m L were weighed and mixed uniformly to obtain a mixed solvent.
(2) Weighing 5mg of carbon nanotubes, adding the carbon nanotubes into a mixed solution of DMF and distilled water, and performing ultrasonic treatment for 3 hours to uniformly disperse the carbon nanotubes in a solvent to obtain a carbon nanotube dispersion solution, wherein the concentration of the carbon nanotubes in the mixed solution is 0.5mg/m L.
(3) 80mg of ferrous oxide tetrahydrate and 66mg of anhydrous sodium acetate are weighed, namely the concentration of the ferrous chloride tetrahydrate is 8mg/m L relative to the concentration of the mixed solution, the molar concentration ratio of the anhydrous sodium acetate relative to the ferrous chloride tetrahydrate is 2:1, the mixed solution is magnetically stirred for 10 minutes, the pH value of the mixed solution is adjusted to 6 by 5 percent HCl, then the mixed solution is put into a 90-degree water bath kettle, the magnetic stirring is continued, the stirring speed is 300 revolutions per minute, and the stirring time is 5 hours.
After cooling, the black product was collected by centrifugal washing with deionized water 3 times and alcohol 3 times. Drying to obtain Fe2O3A carbon nanotube supercapacitor material. The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. Fe2O3A/nanometer carbon tube composite material is characterized in that nanometer Fe2O3The weight ratio of the Fe-Fe alloy in the composite material is 50-60 percent2O3The diameter of the nano particles is less than 10nm, and the nano particles are uniformly loaded on the surface of the carbon nano tube;
the preparation process of the composite material comprises the following steps:
step S1: measuring DMF and distilled water, and uniformly mixing to obtain a mixed solvent;
s2, weighing a certain amount of carbon nanotubes, adding the carbon nanotubes into the mixed solvent prepared in the S1, and uniformly dispersing the carbon nanotubes in the solvent by ultrasonic waves to obtain carbon nanotube dispersion liquid, wherein the concentration of the carbon nanotubes in the mixed liquid is 0.5-2 mg/m L;
step S3, weighing ferrous chloride tetrahydrate and anhydrous sodium acetate, adding the ferrous chloride tetrahydrate and the anhydrous sodium acetate into the carbon nanotube dispersion liquid prepared in the step S2, uniformly stirring and mixing the mixture by magnetic force, adjusting the pH value of the mixed liquid to 6 by HCl with the concentration of 5%, then putting the mixed liquid into a 60-90-degree water bath kettle, and continuing stirring in a water bath manner, wherein the concentration of the ferrous chloride tetrahydrate relative to the concentration of the mixed liquid is 8-12 mg/m L, and the molar concentration ratio of the anhydrous sodium acetate relative to the ferrous chloride tetrahydrate is 2: 1-5: 1;
step S4: cooling, centrifugally cleaning to collect black product, and drying to obtain Fe2O3A carbon nanotube composite material.
2. Fe of claim 12O3The carbon nanotube composite material features that the carbon nanotube is multiwalled one.
3. Fe2O3The preparation method of the/carbon nanotube composite material is characterized by comprising the following steps:
step S1: measuring DMF and distilled water, and uniformly mixing to obtain a mixed solvent;
s2, weighing a certain amount of carbon nanotubes, adding the carbon nanotubes into the mixed solvent prepared in the S1, and uniformly dispersing the carbon nanotubes in the solvent by ultrasonic waves to obtain carbon nanotube dispersion liquid, wherein the concentration of the carbon nanotubes in the mixed liquid is 0.5-2 mg/m L;
step S3, weighing ferrous chloride tetrahydrate and anhydrous sodium acetate, adding the ferrous chloride tetrahydrate and the anhydrous sodium acetate into the carbon nanotube dispersion liquid prepared in the step S2, uniformly stirring and mixing the mixture by magnetic force, adjusting the pH value of the mixed liquid to 6 by HCl with the concentration of 5%, then putting the mixed liquid into a 60-90-degree water bath kettle, and continuing stirring in a water bath manner, wherein the concentration of the ferrous chloride tetrahydrate relative to the concentration of the mixed liquid is 8-12 mg/m L, and the molar concentration ratio of the anhydrous sodium acetate relative to the ferrous chloride tetrahydrate is 2: 1-5: 1;
step S4: cooling, centrifugally cleaning to collect black product, and drying to obtain Fe2O3A carbon nanotube composite material.
4. Fe of claim 32O3The preparation method of the/carbon nanotube composite material is characterized in that in the mixed solvent prepared in the step S1, the volume ratio of DMF to distilled water is 8: 2.
5. Fe of claim 32O3The method for preparing the carbon nanotube composite material is characterized in that in the step S2, the carbon nanotube is a multi-walled carbon nanotube.
6. Fe of claim 32O3The method for preparing a carbon nanotube composite material is characterized in that in step S2, the ultrasonic action time is 3 hours.
7. Fe of claim 32O3The method for preparing a/carbon nanotube composite material, wherein in step S4, a step of centrifugal washing is further included, wherein,
the centrifugal cleaning adopts 3 times of deionized water and 3 times of alcohol centrifugal cleaning, and the speed of a centrifugal machine is 6000 r/min;
after centrifugal cleaning, drying for 12 hours by using a 60-degree oven.
8. Fe of claim 32O3The preparation method of the carbon nanotube composite material is characterized in that in the step S3, the water bath stirring speed is 300 revolutions per minute, the water bath temperature is 60-90 ℃, and the stirring time is 2-5 hours.
9. A supercapacitor, characterised in that Fe as claimed in any one of claims 1 to 2 is used2O3/carbon nanotubes composites or Fe prepared by the process according to any of claims 3 to 82O3The/nanometer carbon tube composite material is used as the cathode material of the super capacitor.
CN201810887727.4A 2018-08-06 2018-08-06 Fe2O3Nano carbon tube composite material, preparation method thereof and super capacitor Active CN109192522B (en)

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